Nu-substituted 1-butene-3, 4-diamines and process for preparing them



Patented May 18, 1948 Glen H. Morey,.

This invention relates to new N-substituted 1-liiitehe"-3', 4-diarni 4" them stituted 1 -butene-,4-di amines of l l "H I ,E H

Amel a. .eiiewoQmmun s-Qimy.inyentiqna airl m alzb teneri A bis-di hsflamin z listens- ,1 -bis-dibutszla me; lxbnt ne-ikhise dIn ;.pr.eparing. the liesubstituted lrvbutene=3,4-

diamines bfnny inventionlrea t.fifliqhlorod-' -.t.1 2'utene.@with a. .vseeendar alkyl ,or: alkeii liiamln lathe, roportionality-at. kastrour molesigot asecondary ne. tonne fn antdi hlbr c mp u I prefer, ihoiuever, to' i s an appreci b e .X

1..of secondafyamine,.forneXamp 50%?ekc ssth is, a, proportiongof abouti'siik moles ormo'r .of secondary ainintb' one mole of 3,4-di-chloro-1- butene to insurep onyersion oi the maximum proportion of dichloro compound to N-substituted sl hutenex zd eniine ,Mnrimarilr; lhyjh rayi enough secondary amine bothtoi rmthe l T-; substitutedgiiaminqggompgr nds arr act with the chlorinelibrated Trom tl'fe 'dichloro compound to "form the amine hydrochloride. This -usei'i'oif excess amine serves to prevent undesir''dijsid 1"fiactionsTfromtaking place with incident reduction in the-yield o he desired lfksubstituted 1- r 153; employing an m'madse g y ikelssevsuiteb es nastier! mteaat ordinary 'roo'm" temperature. the heat of reaction may cause the temperature to rise somewhat and in such cases it is desirable to cool the mixture to maintain the temperature below about 85 C., during the initial stages of Terre ndr, Commercial'SoIi/ents corpora 011,; 11 1;' il pplfi' i p of Man plication da 27,1944,

IND-15.605115" eneral formula is serny em 0;

6 t A-WDIAM NES sno t ante,

.1 s ut atb ibelcw 19mph We a i sothat" cooling must be esoited "to," to prevent the temperatureTro'rnTisiiig too high. Other amines reacgmore slowly, so that no cooling is required. Still others may reactso slowly at 'thatmoderate heating-win be eactio s en ast'o'" the lsloivly reactipg f und'that the'tgm raturi of-the itialistageslfshbuldf" 'Xceed "st" results, although at higher ulnt ities of the desired p ducts a in somewhat lower ield sf" "After part ofthere'ac't iofilh taken blace, hi hrteifip'eralturs apparently-r no hiarm', and ay'evenbeuesi 'le tob irigtl'i''reactioh tosub- A: h 1.-,. Wlienftheieaction appears to be complete, usuall or'several hoursf'd'pending ewhat ontlieltem H ature'ofthereefctionfan ""aqueou'ssolution of a trong basesu'ch"a' s=sodium or potassium hydroxide may b*'added-"to"the "tioii 'niixtur'tdliberatthleeacesssecondary 5a 'rie-"rroifithe hydrogen chloride withwhich it "s combined during the dourse'ofthe reaction, or, if"desirecllthe"crystallinehydrochloride"may filteredfofian'd "the remaining N subs'titut'e'd 1 ridden 'es'; 1212* arts 6f iiiflfaisyiamine in a reaction vessel and allowed to stand. The temperature did not rise above 70 C. After standing overnight, the crystals of amine hydrochloride which formed, were filtered out, and the filtrate was refluxed for a short time, during which additional crystals formed and were filtered out. The reaction mass was then fractionated to remove excess dipropylamine, and the remaining 1-butene-3,4-bis-dipropylamine was rapidly distilled at 5 mm. pressure, resulting in 2'73 parts of product, corresponding to a yield of 53.8%.

EXAMPLE II 1-butene-3,4-bis-dibutylamine Four moles, 500 parts of 3,4-dichloro-1-butene was mixed with 30 moles, 3870 parts of dibutylamine in a reaction vessel, and allowed to stand at room temperature for two days. Then the large mass of crystals of dibutylamine chloride which had formed were filtered off. The filtrate was heated at 45-50 C. for five hours, and the additional crystals which formed were filtered out. The filtrate was then heated to 80 C. and allowed to stand overnight. Additional crystals formed and were filtered out. Then the residue was fractionated at atmospheric pressure to remove excess dibutylamine. The remaining liquid I, product amounted to 675 parts, corresponding to a yield 1-butene-3,4-bis-dibutylamine of 53%.

EXAMPLE III 1 -butene-3,4-bis-dibutylamine Two moles, 250' parts of 3,4-dichloro-1-butene was mixed with 12 moles of dibutylamine, and allowed to stand at room temperature for twentyfour hours. Then the crystals of dibutylamine chloride which had formed were filtered out and the filtrate was heated to boiling under reflux. During this treatment, an additional quantity of crystals formed and were filtered off, combined with the first batch and were washed with 500 parts of dibutylamine to recover entrained product. The washings were added to the original filtrate. The excess dibutylamine was then fractionated off the filtrate at atmospheric pressure.

The remaining liquid was washed substantially free of chlorides and amounted to 317 parts, corresponding to a yield of 1-butene-3,4-bisthe scope of the specification and claims.

What is claimed is: 1. As new compositions of matter N-sub'stituted l-butene-BA-dlamines having the following formula:

HHH

whereinR and R arel members selected from the group consisting of lower alkyl groups and lower alkenyl groups.

2. 1-butene-3,4-bis-dibutylamine.

3. 1-butene-3,4-bis-dipropylamine.

4. In a method for preparing N-substituted 1-butene-3,4-diamines of the class described, the step which comprises reacting a secondary amine selected from the group consisting of lower dialkylamines and lower dialkenylamines with 3,4- dichloro-l-butene in the proportion of at least 4 moles of diamine per mole of 3,4-dichloro-1- butene.

5. In a method for preparing N-substituted 1-butene-3,4-diamines of the class described, the step which comprises reacting a secondary amine selected from the group consisting of lower dialkylamines and lower dialkenylamines with 3,4- dichloro-l-butene in the proportion of at least 6 moles of diamine per mole of 3,4-dichloro-1- butene.

6. In a method for preparing N-substituted 1-butene-3,4-diamines of the character described, the step which comprises reacting a' secondary amine selected from the group consisting of lower dialkylamines and lower dialkenylamines with 3,4-dichloro-1-butene in the proportion of at least 4 moles of disubstituted amine per mole of 3,4- dichloro-l-butene at temperaturesmot exceeding about 85 C.

7. In a method for preparing N-substituted 1-butene-3,4diamines of the character described, the step which comprises reacting a secondary amine selected from the group consisting of lower dialkylamines and lower dialkenylamines with 3,4-dichloro-1-butene in the proportion of at least 6 moles of disubstituted amine'per mole of 3,4- dichloro-l-butene at temperatures not exceeding about 85 C.

8. In a method for preparing 1-butene-3,4- bis-dibutylamine, the stepwhich comprises reacting 3,4-dichloro-1-butene with dibutylamine in the proportion of at least six moles of dibutylamine per mole of 3,4-dichloro-1-butene.

9. In a method for preparing 1-butene-3,4-bisdipropylamine, the step which comprises reacting 3,4-dichloro1-butene with dipropylamine in the proportion of at least six moles of dipropylamine per mole of 3,4-dichloro-1-butene.

10. As new compositions of matter the "1- butene-3,4-bisdiall ylamines, the alkyl groups of which are low molecular groups.

GLEN H. MOREY.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,172,822 Tamele Sept. 12,- 1939 2,216,548 Converse 'Oct.1, 1940 OTHER REFERENCES 'Beilstein, Handbuch der Organische Chemie, 4th ed., vol. IV, 2nd Supp, pages 713-714.

Beilsteln, Handbuch der Organische Chemie, 4th ed., vol. IV, 1st Supp pages423-424.

Bellstein, Handbuch der Organische Chemie,

4thed., page 273. a

Chem. Abstracts, vol. 27, page 3919 (1933). 

